Alkylol cyanamide-polycarboxylic acid condensation product



' in the process.

' or propyl ether of ethylene Patented Mar. 10, 1942 ALKYLOL CYANAMID ACID CONDENS warmr. Ericka, Cos Cob, Cyanamid N. Y., a corporation of No Drawing. Application American E-POLYCARBOXYLIC ATION PRODUCT Serial No.

13 Claims. (Cl. 260-78) This invention relates to condensation prodnets of monoalkylol cyanamides and eir polymers with organic polycarboxylic acids and their anhydrldes and to their methods of preparation.

I have found that a new class of condensation products is obtained when monoalkylol cyanamides or their pohrmers, such as monoethylol cyanamide or diethylol dicyandiamide, are reacted with organic aliphatic or aromatic polycarboxylic acids or their anhydrides.

My new condensation products have an exceedingly complex chemical structure and appear in the form of transparent, viscous, resinous syrups; as sticky, brittle resins; or even as soft or brittle wax-like materials, depending upon the reactants employed They may, if desired, be further reacted with substances such as formaldehyde to form modified resins of value in the fi of cotton textiles, etc. My new condensation products are also ofvalue in the formulation of coating compositions, synthetic waxes, floor polishes, as plasticizers for cellulose acetate.

phenol-formaldehyde, urea-formaldehyde and melamine resins, as adhesive in the preparation of synthetic fibers and laminated materials, and for many other uses which will be evident from their chemical and p y ical-characteristics.

Monoalkylol cyanamides for use in the condensation reaction of my invention may be prepared according to known methods, as for example by treating an aqueous solution of sodium cyanamide with ethylene chlorhydrin at low temperatures followed by neutralization with hydrochloric acid, evaporation, and extraction with an organic solvent. I have also found that the same class of materials is obtained when calcium cye anamide, or other suitable and preferably watersoluble cyanamide compound-is reacted with one or more molecules of an ethylene oxide, propylene oxide, the methyl, ethyl glycol, glycidol, 5.6 anhydro-monoacetone glucose, glucosan, or other compounds containing an alkylene oxide ring or those which provide such a ring structure during the courseof the reaction. .When equimolecular ratios of the cyanamide and an alkylene oxide are reacted a simple alcohol derivative is obtained. but when two or more moles of the alkylene oxide or its hydroxy derivatives are reacted with each mole of the cyanamide there are obtained ether alcohol derivatives including the hydroxy-alkoxalkylol compounds obtained when sugar anhydrides or an excess oi glycidol is used. 65 of alkylene oxide semi-solid resins; as clear or opaque alkylene oxide such as cyanamme is Conn., assignor to comgany, New York,

October 8, 1940, 860,293

I have designated kylol cyanamides.

I have developed an excellent method for the manufacture of monoalkylol cyanamides which may be illustrated in connection with the preparation of monoethylol cyanamide. This process is based on the use of alkali-earth cyanamides, such as calcium cyanamide, together with ethylene oxide, which is relatively cheap and easily available in large quantities. is introduced slowly and with vigorous agitation into water at a temperature not exceeding 30 0., and the mixture is cooled during 30 minutes to 5 C. with continued stirring. An equimolecular amount of ethylene oxide is then introduced slowly into the agitated suspension at a temperature preferably not exceeding 10 0., care being taken that no large excess of ethylene oxide is present at any time.

this latter class as alkoxyal- After all the ethylene oxide has been added the mixture is stirred for 1 hour at a temperature of 1-10 8., the agitation stopped,- the temperature brought up about 25-30 C. within a few hours and the mixture filtered at this temperature and the filter cake washed with water. C0: is passed into the combined flltrate to precipitate the calcium as carbonate which is filtered ofi, and the filtrate is evaporated at low temperatures until a thick, oily syrup is obtained. As the product polymerizes readily high evaporation temperatures should be avoided and it carry out the evaporation under reduced pressures of 10-20 mm. of mercury.

Monoethoxyethylol by using 2 moles of ethylene oxide for each mole of cyanamide in the above process. Monoisopropyl cyanamide is prepared by reacting calcium cyanamide and propylene oxide as described above. Pentahydroxypropoxy-dihydroxy-propyl prepared by the reaction of 6 moles of glycidol O (CQIIEHCHIOH) with one mole of calcium cyanamide.

The exact chemical structure of these compounds may vary with varying conditions of the reaction but I believe that a representative formula is NEG-N-R-OH in which R is either an alkyl or alkoxyalkyl radical, depending on whether one or several moles The calcium cyanamide is preferable to cyanamide may be obtained were reacted with each mole reacted with an organic polycarboxylic acid or.

its anhydride, a condensation takes place which produces waxy or resinous materials having valuable properties. Preferably the reactants are heated to temperatures between 100 and 250 C. whereupon the condensation takes place. It is not always necessary, however, to apply heat to the reactants to cause a condensation to take place. For example, in condensing maleic an-.

hydride with monoethylol cyanamide, it is found that the reaction is of an exothermic character.

The alkylol cyanamides which I have reacted with organic polycarboxylic acids and their anhydrides include monoethylol cyanamide, isopropyl cyanamide, isobutylol cyanamide, isobutoxybutylol cyanamide, pentahydroxypropoxydihydroxypropyl cyanamide and the like.

I have carried out the condensation using a large number of polycarboxylic acids, either allphatic or aromatic, saturated or. unsaturated, containing the diand tricarboxylic groups, the acid anhydrides and even mixtures of these materials. Such acids as succinic, adipic, sebacic, and citric, and the anhydrides of phthalic and maleic acid have been used with good results in the condensation reaction with monoalkylol cyanamides. I believe, therefore, that the condensation is perfectly general in character and will operate with any alkylol cyanamide and any organic polycarboxylic acid to produce condensation products'of the same general type having a wax-like or resinous character.

By varying the molecular ratio of the alkylol cyanamide to the polycarboxyllc acid I have found it possible to control the nature of the condensation product. For example, when 1 mole of monoethylol cyanamide was condensed with 1 mole of phthalic anhydride the product was a hard, non-sticky transparent resin. When 2 moles of monoethylol cyanamide were condensed with 1 mole of phthalic anhydride the resulting product was a pliable, sticky transparent resin. It has also been found possible, and even desirable in some instances, to carry out the condensation in the presence of an inert solvent or diluent such as, for example, xylenon. The formation of lighter colored resins may also be favored by exclusion of air from the reaction zone. This may be accomplished by establishing an atmosphere of an inert gas, as CO2,

Monoethylol cyanamide, one of of illustrationand although certain speciflc despecific examples will be described in connection with the various which follow.

The invention will now be illustrated in greater detail by means of the following specific examples. It should be understood, however, that these examples are given primarily for purposes tails are recited my invention in its broader aspects is'not limited thereto.

Example 1 361 parts by weight of monoethylol cyanamide (90%) and 432 parts of succinic acid, in the molecular ratio of approximately 1:1, were heated slowly with stirring. At a temperature of about 150 C. a white, wax-like intermediate product was formed. Upon further heating to 200 C. a sticky, transparent, viscous, pale-yellow liquid was obtained which upon cooling gave 2..

viscous resin.

( Example 2 361 parts of monoethylol cyanamide (90%) and 584 parts of adipic acid, in the molecular ratio of approximately 1:1, were heated slowly with stirring to 160 C. A clear, pale-yellow liquid was formed which on cooling gave a white,

wax-like material. Upon heating to 260 C. and

cooling the material was a transparent, viscous liquid which on standing became translucent.

Example 3 202 parts monoethylol cyanamide (85%) and 404 parts sebacic acid, in the molecular ratio of approximately 1:1, were heated with stirring for one hour at 125 C. and subsequently at 150- Examplel 66.9 parts isopropylol cyanamide (74.6% solids) and 101.1 parts sebacic acid'and 200 parts of xylenol were charged into a flask equipped with mechanical agitator, condenser, water collector and thermometer and-heated. When the xylenol had melted, stirring was started. After 40 minutes heating and at a temperature of 100 C. CO: was passed through the homogenous liquid. After 80 minutes heating and at a temperature of 213 C. water commenced to collect in the water collector. In 120 minutes, 12.5 parts of water had collected and the operation was discontinued. The reaction mixture was divided into two approximately equal portions.

The flrst portion was subjected to distillations under reduced pressure of 12-18 mm. and at a temperature of 109-170" until all the :wlenol had nitrogen, or mixtures thereof in the reaction vessel.

The waxy and resinous condensation products of my invention are like other resinous materials generally in that their chemical structure is highly complex. I have accordingly not been able to assign structures to them or to classify them with particularity. Nevertheless, the condensation reaction proceeds readily to form characteristic waxy and resinous products having definite physical and chemical properties which minutes.

. phthalic anhydride bility with the product obtained from the first half of the reaction mixture. The use of an inert solvent and of CO: was found to lead to the formation of products of lighter color.

Example Isobutylol cyanamide and sebacic acid in the molecular ratio of 1:1 were heated with agitation for 30 minutes at 180 C. The reaction product was a soft cream-colored, wax-like material, insoluble in cold water but lv'ing in boiling water to give a solution having a pH of approxi-- mately 7.0. The material was also soluble in alcohol but sparingly solublein toluol.

Example 6 Isobutoxy-isobutylol cyanamide (90%) and sebacicacid in the molecular ratio of 1:1 were heated with stirring to 160C. and this temperature maintained for one hour. Upon cooling the product was a soft cream-colored, wax-like material insoluble in cold water, sparingly soluble in toluene and fairly soluble in ethyl alcohol.

When a smaller proportion of isobutoxy isobutylol c'yanamide was .used the product became harder. Thus, when 76 parts of isobutoxy-isobutylol cyanamide were reacted with 202 parts of sebacic acid at 180 C. for one half hour the product on cooling to room temperature was a hard brittle wax.

Example 7 287 parts monoethylol 'cyanamide (90%) and 385 parts citric acid in the molecular ratio of 3 moles monoethylolcyanaznide to 2 moles citric acid, were heated with stirring at 120C. for Upon cooling a colorless semi-solid sticky resin was formed which /was sparingly soluble in cold water and gfairly soluble in hot water and hot alcohol. i

Q Example 8 Example -9 380 parts monoethylol cyanamide and 296 parts phthalic anhydride in the approximate molecular ratios of 2 moles of monoethylol cyana mide to 1 mole .phthalic anhydride, were heated slowly with stirring to 130 C. The resulting product was a sticky, transparent, pale-yellow resin. Upon further heating to 230 C. the product became amber-colored but'remained a sticky transparent resin.

Example 10 38 parts monoethylol cyanamide. 59 parts and 31 parts of monoethylol cyanamide-succin'ic acid condensation product prepared as injthe first part of Example 1 were slowly heated to 160 C. The product was a solid, flexible, transparent resin.

insoluble in hot water and 7 condensation product of Example 11 38 parts monoethylol cyanamlde and 19.6 parts maleic anhydride in the molecular ratio of approximately 4 moles of monoethylol cyanamide for 1 mole of maleic anhydride were stirred together without heating. An exothermic reaction was found to take place and the temperature rose to C. When the reaction had subsided and cooled the product was found to be an ambercolored sticm resin which dissolved in water to give a solution alkaline to litmus.

Example 12 1 mole of pentahydroxypropoxy-dihydroxypropylcyanamide and 2 moles succinic acid were heated with stirring to about C. and reacted .at this temperature for one half hour. Upon cooling the product was an ambercolored, transparent, stich resin soluble in hot water and alcohol and insoluble in toluene.

What I claim is: Y

1. A composition of matter comprising the condensation product of a member of the group consisting of polycarboxylic acids and their anhydrides with a member of alkylolcyanamides and their polymers.

2. A composition of matter comprising the condensation product of a member of the group consisting of polycarboxylic acids and their anhydrides with monoethylol cyanamide.

3. A composition oi matter comprising the condensation product of a dicarboxylic acid with a member of the group consisting of alkylol cyanamides and their polymers.

4. A composition of matter comprising the vcondensation product of an aromatic dicarboxylic acid with a member of the group consisting of alkylol cyanamides and their polymers.

5. A composition of matter comprising the condensation product of an aliphatic dicarboxylic acid with a member of the group consisting of alkylol cyanamides and their polymers.

6. A composition of matter comprising the condensation product of an aliphatic dicarboxylic acid with monoethylol cyanamide.

7. A composition of matter comprising the succinic acid with monoethylol cyanamide.

8. A composition of matter comprising the condensation product of phthalic anhydride with monoethylol cyanamide.

9.11 composition of matter comprising the condensation product of sebacic acid with monoethylol cyanamide.

10. A method of their anhydrides with a member of the group consisting of allwlol cyanamides and their polymers.

11. A method of producing waxy and resinous materials which comprises reacting a member of the group consisting of polycarboxylic acids and their anhydrides with monoethylol cyanamide.

12. A method of producing wax-like materials which comprises reacting monethylol cyanamide b which comprises reacting with sebacic acid.

13. A method of producing resin-like materials 7 monethylol cyanamide with phthalic anhydride.

'WALTER P. narcxsoi, the group consisting producing waxy andresinous materialswhich comprises reacting a member of the group consisting of polycarboxylic acids and 

